Organochlorosilane and dipodal silane compounds

ABSTRACT

Processes are provided for producing organchlorosilanes and dipodal silanes in which an organic halide or alkene or chloralkene is reacted with a hydridochlorosilane in the presence of a quaternary phosphonium salt catalyst by providing sufficient heat to effect a dehydrohalogenative coupling reaction and/or a hydrosilylation reaction and venting the reaction to control reaction pressure and to remove gaseous byproducts from the reaction. The processes are preferably continuous using a catalyst in fluid form at reaction pressures not exceeding about 600 psi. The reactions may be carried out substantially isothermally and/or isobarically, for example in a plug flow reactor or continuous stirred tank reactor. The processes may produce novel silylated compounds including 1,2-bis (trichlorosilyl)decane or 1,2-bis (trimethoxysilyl)decane.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of copending U.S. application Ser. No.10/856,194, filed May 28, 2004, now allowed, which claims the benefit ofU.S. provisional patent application 60/474,440, filed May 30, 2003, thedisclosures of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

This invention relates to processes, including continuous processes, forthe production of silylated derivative compounds of organic halides andalkenes, including organochlorosilanes and dipodal silanes, useful in avariety of applications including as coupling agents and as surfacemodifiers of substrates related particularly to water repellency anddiagnostic applications.

It has been reported in U.S. Pat. No. 6,392,077 of Jung, et al. thatorganochlorosilanes can be prepared in a batch process by adehydrohalogenative coupling reaction of an alkyl halide with a hydridofunctional chlorosilane in the presence of a solid phosphonium catalystor solid supported catalyst, as further described in U.S. Pat. No.4,613,491 of Jung, et al.

In a similar manner, dipodal silanes are produced either in a two stepprocess in which the dehydrohalogenative coupling reaction of an alkenewith a chlorosilane occurs, first immediately followed by ahydrosilylation reaction or in two hydrosilylation steps. However, thisreaction also requires the use of a solid catalyst or solid supportedcatalyst. This process also requires charging a solid catalyst to abatch reactor and, once the reaction is complete, removing the catalystfrom the reaction mixture either by filtration or distillation. On acommercial scale, this is a labor- and time-consuming operation.

The reactions reported by Jung are carried out in sealed tube reactorsat estimated pressures that exceed 1000 p.s.i. The use of sealed tubereactors also causes redistribution of initial by-products of thereaction resulting in such hazardous materials as dichlorosilane andsilane.

Prior to the present invention, the reaction of alkyl halides andhydridochlorosilanes was commercially carried out by a batch process,which included a dehydrochlorinative coupling reaction in the presenceof an amine base acceptor and sometimes a copper catalyst (Benkesser etal, J. Am. Chem. Soc., 91 (13):3666-67 (1969); Furuya et al, J.Organomet. Chem., 96: C1-C3 (1975); Corriu et al., J. Organometal.Chem., 562:79-88 (1998)). This is a cumbersome process which requiresreacting a chlorosilane with a stoichiometric amount of an amine, whichgenerates a considerable amount of waste by-products. This process alsogenerates amine hydrochloride salts which must be removed by filtration.Amine hydrochloride salts are difficult to filter and are often solublein the product. As a result, further filtration after productpurification is required, and still the amine hydrochloride saltscontinue to drop out of solution after the products have been standingfor extended periods of time.

Thus, the large scale production of organochlorosilanes and dipodalsilanes by the above mentioned batch process is cumbersome, expensiveand, in the case of the Benkesser process, generates excessive waste,such as amine hydrochloride salts and, in the Jung process, is subjectto significant by-product generation, attributed to prolonged exposureto the catalyst at elevated temperatures and pressures resulting in theformation of by-products, such as dichlorosilane and silane gas whichare difficult to handle and pyrophoric.

BRIEF SUMMARY OF THE INVENTION

To solve the shortcomings described in the prior art for producingorganochlorosilanes, dipodal silanes and other silylated compounds, thepresent invention provides processes, including continuous typeprocesses, which comprise reacting a hydridochlorosilane compound witheither an organic halide or an alkene in the presence of a quaternaryphosphonium salt catalyst, preferably in fluid form, resulting in moreefficient processes that overcome many of the shortcomings associatedwith known processes for producing the same or similar compounds.

According to a first process of the present invention,organochlorosilanes are produced by mixing a hydridochlorosilane, anorganic halide and a quaternary phosphonium salt catalyst, providingsufficient heat to effect a dehydrohalogenative coupling reaction of thehydridochlorosilane with the organic halide, and venting the reaction tocontrol reaction pressure and to remove gaseous byproducts from thereaction.

According to a second process of the present invention, dipodal silanesare produced by mixing a hydridochlorosilane, an alkene and a quaternaryphosphonium salt catalyst, providing sufficient heat to effect a doublehydrosilylation reaction of the alkene with the hydridochlorosilane, andventing the reaction to control reaction pressure and to remove gaseousby products from the reaction.

Although the processes of the invention could be carried out as batchreactions, it is preferred and a particular advantage of the processesof the invention that they be carried out continuously for maximumthroughput of the reactants and ease of scalability of the reactions tocommercial processes. Suitable reactors for carrying out the continuousprocesses include plug flow reactors and continuous stirred tankreactors.

The catalyst is preferably in fluid form for ease of introducing thecatalyst into the reaction system and maintaining contact with thereactants. The fluid form may include, for example, a homogeneoussolution, a liquid catalyst, a molten catalyst, or even possibly aslurry of finely divided catalyst powder. Alkyl phosphonium chloridesare the preferred catalysts.

The processes are preferably carried out substantially isothermally,i.e., at constant temperature, and substantially isobarically, i.e., atconstant pressure. Moreover, the processes are carried out at relativelylow pressures, namely less than 1,000 p.s.i., and preferably not greaterthan about 600 p.s.i.

In order to produce good product yields, it is important to keep theresidence time of the reactants in the reaction zone short. In the caseof producing organochlorosilanes, the residence time in a reactor shouldpreferably be not greater than about two hours, in order to keepundesirable byproduct formation to a minimum. In the case of producingdipodal silanes, the residence time in the reactor should preferably notbe greater than about five hours, for the same reasons.

The processes of the present invention provide a viable access to newbuilding blocks for various silylated materials, for example, byproviding a simple, commercially scalable process for making alkylsilanes which can be converted to further products. In the case ofdipodal silanes, the second process of the present invention provides acommercially scalable process for producing bis (chlorosilyl)derivatives, for which no other commercially satisfactory process ispresently available.

The invention also provides novel silyl derivatives, namely1,2-bis(trichlorosilyl)decane and 1,2-bis (trimethoxysilyl)decane, andmethods of making the same.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

The foregoing summary, as well as the following detailed description ofthe invention, will be better understood when read in conjunction withthe appended drawings. For the purpose of illustrating the invention,there are shown in the drawings embodiments which are presentlypreferred. It should be understood, however, that the invention is notlimited to the precise arrangements and instrumentalities shown. In thedrawings:

FIG. 1 is a simplified flow diagram of a continuous process forpreparing silylated alkyl derivative compounds utilizing a continuousplug flow reactor (PFR) in accordance with a first embodiment of theinvention; and

FIG. 2 is a simplified flow diagram of a continuous process forpreparing silylated alkyl derivative compounds utilizing a continuousstirred tank reactor (CSTR) in accordance with a second embodiment ofthe invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to processes, including continuousprocesses, for the production of silylated derivative compounds oforganic halides and alkenes, including organochlorosilanes and dipodalsilanes, useful in a variety of applications including as couplingagents and as surface modifiers of substrates related to waterrepellency and diagnostic applications. More specifically, thisinvention includes processes in which a quaternary phosphonium saltcatalyst, preferably an alkyl phosphonium chloride catalyst, is used,preferably in fluid form, such as dissolved in a solvent, and combinedwith a hydridochlorosilane and either an alkyl halide or an alkene toform silylated derivative compounds.

Various types of reactors are within the scope of the invention,including continuous plug flow reactors and continuous stirred tankreactors, such that the processes have relatively short residence timesand minimal side reactions. The reactor's pressure is dictated by thevapor pressure of the reactants at the reaction temperature. Gaseousby-products, including hydrogen, hydrogen chloride, tetrachlorosilanes,and dichlorosilanes, are allowed to vent in order to control reactionpressure and preferably maintain a constant reaction pressure.

A particular advantage of the present invention is that it provides acontinuous process for the dehydrohalogenative coupling reaction ofhydrido functional chlorosilanes with alkyl halides and alkenes in thepresence of a homogeneous phosphonium catalyst solution. The inventionalso allows the production of dipodal silanes by the doublehydrosilylation of alkenes, preferably to produce vicinal disilylderivatives.

Still further, the invention allows the production of silane products atrelatively low or moderate pressures, for example less than 1000 p.s.i.In so doing, this invention controls the exposure of reactants tocatalyst at elevated temperatures and minimizes or eliminates by-productformation.

The processes of the present invention provide greater flexibility inproducing organochlorosilanes and dipodal silanes, using relativelyshort residence times, reducing the amount of waste generated, andallowing recycle of the catalyst. This in turn provides a process withimproved process economics on a commercial scale. As a result, thisinvention provides the ability to produce organochlorosilanes anddipodal silanes on a continuous basis by processes which are moreefficient than those of the prior art.

Particularly preferred is the use of the processes of this invention toproduce 1,2-disilyl derivatives of alkenes which have utility ascoupling agents and as surface modifiers of substrates for waterrepellency and in diagnostic applications.

Stated otherwise, the present invention relates to processes, includingcontinuous processes, for preparing silyl and disilyl derivativecompounds of organic halides and alkenes, including organochlorosilanesand dipodal silanes, wherein the processes comprise adehydrohalogenative coupling of hydridochlorosilanes with either theorganic halide or the alkene in the presence of a quaternary phosphoniumsalt catalyst. Where the processes of this invention involve reacting analkene with a hydridochlorosilane, it is understood that thedehydrohalogenative coupling reaction is followed by a hydrosilylationreaction to produce, silylated derivative compounds, including vicinaldisilyl derivative compounds, of the alkene.

Dehydrochlorinative coupling reactions for preparing organochlorosilanesare known in the art, for example from U.S. Pat. No. 6,392,077 of Junget al and Kang, Seung-Hyun et al, “Phosphonium Chloride-CatalyzedDehydrochlorinative Coupling Reactions of Alkyl Halides withHydridosilanes,” Organometallics, 22:529-534 (2003), the disclosures ofwhich are incorporated herein by reference. The processes of the presentinvention can use virtually any of the hydridochlorosilanes (also knownas “hydrochlorosilanes”) and organic halides to produce virtually any ofthe organochlorosilanes disclosed by Jung et al and Kang et al in thesereferences, as well as others which will be apparent to those skilled inthe art based on the present disclosure.

Examples of dehydrochlorinative coupling reactions and doublehydrosilylation reactions are shown below. These and other relatedreactions may be carried out according to the processes of the presentinvention.

The Jung Reaction

Dehydrochlorinative without base acceptor

Dehydrochlorinative coupling with Methylhydridosilane

Double Hydrosilylation

Dehyrochlorinative Coupling

Catalyst: (tetradecyl)tributylphosphonium

Stirred Autoclave; Catalyst: (tetradecyl)tributylphosphonium C1

Catalyst: tetrabutylphosphonium chloride/toluene

Double Hydrosilylation

Catalyst: tetradecyltributylphosphonium chloride

The dehydrohalogenative coupling and hydrosilylation reactions describedherein are accomplished by heating and mixing the reactants and productsin the process as described in more detail below. Preferably, thedehydrohalogenative coupling reactions that occur in the processes ofthis invention are completed at a rate that maintains no more than a twohour residence time, most preferably the residence time is about onehour, while the hydrosilylation reactions may require up to about fouror five hours of residence time. Also, preferably, the reaction iscarried out at a temperature from about 100° C. to about 200° C., mostpreferably from about 120° C. to about 150° C.

Further, while the pressure of the process results from the vaporpressure of the reactants at the reaction temperature, the reaction ismaintained at a nearly constant pressure of less than about 1,000 p.s.i.Preferably, the reaction is performed at a pressure of about 50 p.s.i.to about 600 p.s.i., most preferably from about 350 p.s.i. to about 400p.s.i. It is also preferred that the reactions that result from theprocesses of this invention take place in an inert atmosphere,preferably nitrogen gas. However, it will be recognized by those ofordinary skill in the art from this disclosure that other inert gasescould be used, if desired, without departing from the spirit of theinvention.

Preferred in the processes of this invention are alkyl phosphoniumchloride catalysts, preferably dissolved in an organic solvent toproduce a phosphonium chloride catalyst solution. The phosphoniumchloride catalyst used in this invention may be, for example,tetrabutylphosphonium chloride, trihexylbutylphosphonium chloride,(tetradecyl)tributylphosphonium chloride, benzyltributylphosphoniumchloride, tetramethylphosphonium chloride, tetraethylphosphoniumchloride, benzyltriphenylphosphonium chloride, or ethylenebis(benzyldimethylphosphonium chloride). Preferably, the phosphoniumchloride catalyst is an alkyl phosphonium chloride catalyst. Mostpreferably, the catalyst is selected from the group consisting oftetrabutylphosphonium chloride, trihexylbutylphosphonium chloride, and(tetradecyl)tributylphosphonium chloride. The catalysts described can bedissolved in several different organic solvents including, but notlimited to, toluene, diethylbenzene, hexane, tetrahydrofuran, andacetonitrile. However, it will be recognized by those of ordinary skillin the art from this disclosure that other types of solvents, known inthe art or to be discovered in the art, could be used, if desired,without departing from the spirit of the invention provided that thesolvent is capable of dissolving the selected catalyst and does notadversely affect the reaction.

In a typical preparation, a solid alkyl phosphonium chloride catalyst isdissolved in a suitable solvent, for example toluene, to form ahomogeneous solution of liquid or molten alkyl phosphonium chloridecatalyst. Preferably, the alkyl phosphonium chloride catalyst, oncedissolved, remains in solution. Ultimately, a catalyst which is liquidat process conditions, such as trihexylbutylphosphonium chloride, may beused.

Preferred hydridochlorosilanes for use in the invention includetrichlorosilane, methyldichlorosilane and dichlorosilane. Mostpreferably, the hydridochlorosilane is trichlorosilane. However, it willbe recognized by those of ordinary skill in the art from this disclosurethat other chlorosilanes could be used, if desired, without departingfrom the spirit of the invention.

The organic halides may contain an alkyl, allyl or aryl functionalgroup. Exemplary organic halides include, but are not limited to, allylchloride, allyl bromide, crotyl chloride, benzyl chloride,1-chlorooctane, 1-chloro-3,3,3-trifluoropropane,(chloromethyl)trichlorosilane, (chloromethyl)dichlorosilane,(chloromethyl)trimethylsilane, (3-chloropropyl)trimethylsilane,4-fluorobenzyl chloride, 4-chlorobenzyl chloride, 4-methoxybenzylchloride, 4-phenylbenzyl chloride, 1-chloroethylbenzene,cyclopentylchloride, 2-chlorobutane, isopropyl chloride,dichloromethane, 1,2-dichloroethane, 1,3-dichloropropane,1-bromo-3-chloropropane, 1,4-dichlorobutane, and1,4-bis(chloromethyl)benzene. Preferably, the organic halide is eitherbenzyl chloride or allyl chloride.

The alkene may be particularly selected from various olefins or maycontain an allyl or aryl functional group. Exemplary alkenes include,but not limited to, ethylene, propylene, 1-butene, 2-butene,isobutylene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene,1,2-dichloroethene, 1,2-dibromoethene, 1-bromo-1-chloropropene,2-bromo-1-chloropropene. Preferably, the alkene is 1-decene.

After the phosphonium chloride catalyst is dissolved in a suitablesolvent, the catalyst solution is mixed with a hydridochlorosilane andeither an organic halide or an alkene. The amount of hydridochlorosilaneused is substantially equivalent to or more than, preferably 2 to 3times, the amount of organic halide or alkene. The amount of phosphoniumchloride catalyst used is sufficient to catalyze the reaction tocompletion, generally, a 0.02 to 0.1 mole ratio, preferably a 0.05 moleratio, relative to the amount of organic halide or alkene.

Referring now to the drawings, there are shown in FIGS. 1 and 2preferred embodiments of the invention for preparing silylatedderivative compounds of organic halides or alkenes (exemplified in FIGS.1 and 2 as an “olefin”), including organochlorosilane and dipodal silanecompounds. More specifically, FIG. 1 shows a continuous process in whichan alkylphosphonium chloride catalyst, an olefin or an alkyl chloride,and trichlorosilane are reacted in an isothermal plug flow reactor (PFR)to produce silylated alkyl derivatives of either the olefin or the alkylchloride.

The process shown in the embodiment of FIG. 1 includes first dissolvingthe alkylphosphonium chloride catalyst in one of the solvents previouslymentioned after which the catalyst solution is combined with thereactants of trichlorosilane and either an alkyl chloride or an alkene.Preferably, the reactants and the catalyst solution are mixed by astatic mixer. However, it will be recognized by those of ordinary skillin the art from this disclosure that other types of mixers could beused, if desired, without departing from the spirit of the invention. Itwill also be recognized by those skilled in the art from the presentdisclosure that the process can be operated effectively using dual feedpumps (not shown) for feeding the reactants and the catalyst solution tothe reactor.

The combination of trichlorosilane, alkyl chloride or alkene, andcatalyst solution proceed to a first heat exchanger which increases thetemperature of the reactants and catalyst solution from about roomtemperature to, preferably, about 100° C. to about 200° C.

Referring still to FIG. 1, trichlorosilane, the catalyst solution andthe alkyl chloride or alkene enter a continuous reactor which is anisothermal plug flow reactor (PFR). Preferably, the isothermal PFR is acontinuous PFR containing more than one heating zone and at least onemixing zone. Most preferably, the isothermal PFR is a continuousisothermal PFR which comprises three heating zones such that Zone 1heats the reactants and catalyst solution, Zone 2 mixes the reactantsand catalyst solution, and Zone 3 cools the reactants and catalystsolution. Also, preferably, Zone 2 comprises a plurality of staticmixing elements.

The isothermal PFR is provided with a back pressure regulating valve(not shown) which maintains the process, including the continuousreactor, at the desired constant reaction pressure. Preferably, thepressure in the reactor is maintained between 50 p.s.i. and 600 p.s.i.,most preferably from about 350 p.s.i. to about 400 p.s.i., and thetemperature in the reactor is maintained at the temperature establishedby the first heat exchanger which, as previously stated, is preferablyabout 120° C. to about 200° C.

After passing through the reactor, the reaction products and catalystsolution pass through a second heat exchanger which returns the productsto about room temperature before entering a holding vessel. The holdingvessel has attached, toward the top of the vessel, a gas discharge pipewhich allows by-product and inert gases to vent from the holding vesselthereby assisting the process, including the continuous reactor, tooperate at a constant reaction pressure. The gas discharge pipe isconnected to an inert gas inlet pipe which provides inert gas, which ispreferably nitrogen, to the gas discharge pipe. Inert gas allows theprevention of further undesired reactions in the holding vessel.

The gas discharge pipe is also connected to a scrubber (not shown). Thescrubber permits scrubbed gases including, for example, hydrogen andhydrogen chloride, to be safely removed from the process. The scrubbercan be of a variety of types and designs including, but not limited to,single or multiple stage types and horizontal or vertical flow design.However, the design of the scrubber should be based on a determinationof several factors, including the chemical composition of the by-productgases discharged from the holding vessel. Preferably, the scrubber is anacid gas scrubber.

The holding vessel also has attached, toward the bottom of the vessel, aholding vessel discharge pipe where the reaction products, which aresilylated alkyl derivative compounds of the alkene or alkyl chloride,are removed from the process.

Referring now to FIG. 2, a second preferred embodiment of the inventionis shown whereby a process is disclosed that is similar to the processdescribed in the first preferred embodiment. The second preferredembodiment, as shown in FIG. 2, is a continuous process in which analkylphosphonium chloride catalyst, an olefin or an alkyl chloride, andtrichlorosilane are reacted in continuous stirred tank reactor (CSTR) toproduce silylated alkyl derivatives of either the olefin or the alkylchloride. The process includes first dissolving the alkylphosphoniumchloride catalyst in one of the solvents previously mentioned afterwhich the catalyst solution is combined with the reactants oftrichlorosilane and either an alkyl chloride or an alkene. Preferably,the reactants and the catalyst solution are pumped to a mixing vessel(not shown), which is preferably a static mixer. However, as previouslystated, it will be recognized by those of ordinary skill in the art fromthis disclosure that other types of mixers could be used, if desired,without departing from the spirit of the invention. Again, it will alsobe recognized by those skilled in the art from the present disclosurethat the process can be operated effectively using dual feed pumps (notshown) arranged in series or parallel for feeding the reactants and thecatalyst solution to the reactor.

The combination of trichlorosilane, alkyl chloride or alkene, andcatalyst solution proceed to the CSTR, which is preferably a constantpressure isothermal CSTR, after passing a first pressure gauge and afirst temperature gauge, which determines the pressure and temperatureof the reactants and catalyst solution. The CSTR increases thetemperature of the reactants and catalyst solution from about roomtemperature to, preferably, about 100° C. to about 200° C.

The CSTR has attached, toward the top of the reactor, a gas dischargepipe which allows by-product and inert gases to vent from the CSTRthereby assisting the process, including the reactor, to operate at aconstant reaction pressure. Similar to the first preferred embodiment,the gas discharge pipe is connected to an inert gas inlet pipe whichprovides inert gas, which is preferably nitrogen, to the gas dischargepipe, for purging and blanketing the holding vessel and dilutingpotentially pyrophoric byproducts below ignition limits.

The gas discharge pipe is also connected to a scrubber (not shown). Thescrubber permits scrubbed gases including, for example, hydrogenchloride and chlorosilanes, to be safely removed from the process. Thescrubber can be of a variety of types and designs including, but notlimited to, single or multiple stage types and horizontal or verticalflow design. Again, the design of the scrubber should be based on adetermination of several factors, including the chemical composition ofthe by-product gases discharged from the holding vessel. Preferably, thescrubber is an acid gas scrubber.

The CSTR also has attached, toward the bottom of the reactor, adischarge pipe which allows the reaction products, which are silylatedalkyl derivative compounds of the alkene or alkyl chloride, and thecatalyst solution to discharge to a heat exchanger before being removedfrom the process. Preferably, the pressure in the CSTR is maintainedconstant in a range from about 50 p.s.i. to about 600 p.s.i. The heatexchanger returns the reaction products to about room temperature.

It will be recognized by those of ordinary skill in the art from thisdisclosure that other embodiments of this invention are possibleincluding, for example, arranging a PFR and a CSTR in series, ifdesired, without departing from the spirit of the invention. It willalso be recognized by those of ordinary skill in the art from thisdisclosure that, where a PFR and a CSTR are arranged in series, pipingarrangements and alignments can be such that only one reactor is usedwhile the other is bypassed in order to, for example, repair thebypassed reactor.

The invention will now be described in conjunction with the followingspecific, non-limiting examples. Unless otherwise stated, allpercentages are percentages by weight.

EXAMPLE 1

This example describes a reactor design which is a continuous PFR havingthree heating zones, such as described above in connection with FIG. 1.More specifically, the heating zones are: Zone 1 which pre-heats thereactants to 180° C.; Zone 2 which has a volume of 2851.7 milliliterequipped with 24 static mixing elements and maintains the reactionmixture at 180° C. for the desired residence time; and Zone 3 whichreduces the reaction mixture temperature from the reaction temperatureto room temperature. Trichlorosilane, benzyl chloride and a 50% solutionof tetradecyltributylphosphonium chloride in toluene are fed to the PFRreactor by a dual feed pump in a 3:1:0.1 molar ratio, respectively, at arate molar to maintain a one hour residence time in the reactor. Thereaction pressure is adjusted by utilizing a back-pressure regulatingvalve set to 350 p.s.i. The reaction products are collected in a vesselwhich allows a by-product of hydrogen chloride to be vented to an acidgas scrubber. A gas chromatogram (GC) of the reaction mixture revealsthat the mixture is composed of 61.2 weight percentbenzyltrichlorosilane and a balance of tetrachlorosilane and toluene.

EXAMPLE 2

By utilizing the same reactor, ancillary equipment and procedure as inExample 1 above, trichlorosilane, 1-decene andtetradecyltributylphosphonium chloride 50% in toluene are fed in a2:1:0.1 molar ratio, respectively, at a rate to maintain a two hourresidence time. As in Example 1, the reaction mixture is maintained at atemperature of 180° C. and a pressure of 350 p.s.i. The reaction mixtureis collected in a vessel which allows a by-product of hydrogen chlorideto be vented to an acid gas scrubber. A gas chromatogram of the reactionmixture shows that the mixture is 5.4 weight percentdecyltrichlorosilane, 70.3 weight percent 1,2-bis(trichlorosilyl)decane(a novel compound), trichlorosilyldichlorosilyldecane isomers, and abalance of tetrachlorosilane and toluene.

EXAMPLE 3

By utilizing the same reactor, ancillary equipment and procedure asExample 1 above, trichlorosilane allyl chloride andtetrabutylphosphonium chloride 50% in toluene are fed in a 2:1:0.05molar ratio, respectively, at a rate to maintain a one hour resistancetime. Zone 2 of the reactor maintains the temperature of the reactionmixture at 130° C., and the pressure in the reactor is adjusted bysetting the back-pressure regulated valve to 150 p.s.i. to 200 p.s.i.The reaction mixture is collected in a vessel which allows the hydrogenchloride by-product to be vented to an acid gas scrubber. A gaschromatogram of the reaction mixture shows that the mixture was 48 wt%allyltrichlorosilane, 3 wt% chloropropyltrichlorosilane and 2 wt%1,3-bis(trichlorosilyl)propane, the balance being composed oftetrachlorosilane and toluene.

EXAMPLE 4

Trichlorosilane, allyl chloride and tetrabutylphosphonium chloride 50%in toluene are fed to a continuous isothermal 5 gallon CSTR of the typeshown in FIG. 2 in a 2:1:0.05 molar ratio, respectively, at a rate tomaintain a one hour residence time in the reactor. The reactor isoperated at a temperature of 130° C., and a back-pressure regulatingvalve was set at a pressure of 350 p.s.i. to control reaction pressure.A hydrogen chloride gas by-product is continuously vented to an acid gasscrubber, while the liquid phase reaction products are continuouslyremoved from the reactor via a heat exchanger to bring the mixture toroom temperature, before being collected in a vessel. A gas chromatogramof the reaction mixture shows that the mixture is 45 weight percentallyltrichlorosilane, 5 weight percent 1,3-bis(trichlorosilyl)propane, 3weight percent chloropropyltrichlorosilane, and a balance oftetrachlorosilane and toluene.

EXAMPLE 5

This example demonstrates the formation of1,2-bis(trimethoxysilyl)decane (a novel compound) by reacting a1,2-bis(trichlorosilyl)decane and 1-trichlorosilyl-2-dichlorosilyldecanemixture, such as obtained in Example 2, with trimethylorthoformate andmethyl alcohol, using chloroplatinic acid (catalyst) and tetrahydrofuranin a 3-liter 4 neck flask equipped with a magnetic stirrer, potthermometer, addition funnel and reflux condenser. The reactor wascharged with 936.8 grams of 1,2-bis(trichlorosilyl)decane and1-trichlorosilyl-2-dichlorosilyldecane mixture and heated to 40° C.Trimethylorthoformate was added to the flask at a rate to control theevolution of methyl chloride. The reaction mixture was heated to 150° C.and then allowed to cool to 80° C., at which point 160.2 milliliters ofmethyl alcohol and 1 milliliter of 5 percent chloroplatinic aciddissolved in tetrahydrofuran were added to the reactor flask and heatedto 120° C. for 2 hours. The reaction mixture was distilled and yielded624 grams of 1,2-bis(trimethoxysilyl)decane having a boiling point of132° C. at 0.4 millimeters Hg, a density of 0.984 at 20° C., and arefractive index of 1.4303 at 20° C.

While Examples 1-4 above demonstrate continuous processes according tothe invention, the following Examples 6-11 are batch processes, whichnevertheless demonstrate the potential for commercial scalability withthe processes of the invention.

EXAMPLE 6

A 1 liter high pressure reactor equipped with overhead stirring, anadjustable pressure relief valve and a thermowell was charged with 126.4grams of 1-decene, 370 grams of trichlorosilane and 58.6 grams of a 50weight percent tetrabutylphosphonium chloride in toluene solution. Thepressure relief valve was set to vent at 350 p.s.i., and the reactionmixture was heated to 200° C. for a period of 5 hours. A gaschromatogram which revealed that the reaction products were primarilycomposed of 5.4 weight percent decyltrichlorosilane and 70.3 weightpercent of 1,2-bis(trichlorosilyl)decane, which is a novel compound.

EXAMPLE 7

A 1 liter high pressure reactor equipped with overhead stirring, anadjustable pressure relief valve and a thermowell was charged with 126.4grams of 1-decene, 370 grams of trichlorosilane and 28 grams of(tetradecyl)tributylphosphonium chloride. The pressure relief valve wasset to vent at 600 p.s.i., and the reaction mixture was heated to 200°C. for a period of 6 hours. It was observed that a positive pressure inthe reactor was not generated until the reaction temperature reachedabout 195° C. A gas chromatogram revealed that the reaction productswere primarily composed of 13.2 weight percent decyltrichlorosilane and57 weight percent 1,2-bis(trichlorosilyl)decane.

The above reaction was repeated at different parameters as indicatedbelow with the corresponding conversions and yields shown. Pressure TempTime Conversion RSiCl₃ R(SiCl₃)(SIHCl₂) R(SiCl₃)₂ (atm) (° C.) (hr)HSiCl₃:C₁₀H₂₀ (%) (%) (%) (%) 43.3 180 1 3:1 >99 18.3 2.5 79.2 23.3 2005 3:1 91.6 7.2 5.7 87.1 23.3 200 4 4:1 96.3 25.2 5.4 68.5

EXAMPLE 8

A 1 liter high pressure reactor equipped with overhead stirring, anadjustable pressure relief valve and a thermowell was charged with 115.3grams of benzyl chloride, 370 grams of trichlorosilane and 27 grams of(tetradecyl)tributylphosphonium chloride dissolved in 56 grams oftoluene. The pressure relief valve was set to vent at 350 p.s.i., andthe reaction mixture was heated to 150° C. for a period of 1 hour. A gaschromatogram revealed that the reaction products contained 35.9 weightpercent benzyltrichlorosilane.

EXAMPLE 9

A 1 liter high pressure reactor equipped with overhead stirring, anadjustable pressure relief valve and a thermowell was charged with 148.2grams of allyl chloride, 524.7 grams of trichlorosilane and 57.1 gramsof a 50 weight percent (tetradecyl)tributylphosphonium chloride intoluene solution. The pressure relief valve was set to vent at 400p.s.i. and the reaction mixture was heated to 130° C. for a period of 2hours. A gas chromatogram revealed that the reaction mixture wascomposed of 48 weight percent allyltrichlorosilane and 1.5 weightpercent of 1,3-bis(trichlorosilyl)propane.

EXAMPLE 10

A 1 liter high pressure reactor equipped with overhead stirring, anadjustable pressure relief valve and a thermowell was charged with 148.2grams of allyl chloride, 524.7grams of trichlorosilane and 114.2 gramsof a 50 weight percent (tetradecyl)tributylphosphonium chloride intoluene solution. The pressure relief valve was set to vent at 400p.s.i., and the reaction mixture was heated to 130° C. for a period of 2hours. A gas chromatogram revealed that the reaction mixture wascomposed of 3 weight percent allyltrichlorosilane and 15 weight percentof 1,3-bis(trichlorosilyl)propane.

EXAMPLE 11

A 1-gallon reactor, equipped with a pressure relief valve, was chargedwith 807.2 grams of chloromethyltrichlorosilane, 1,185.0 grams oftrichlorosilane and 129 grams of trihexyltetradecylphosphonium chloride.The pressure relief valve was set to 650 psi and the reaction mixturewas heated to 150 ° C. Once the reaction mixture reached 50 ° C., anexothermic reaction initiated and caused a very rapid temperature riseas well as pressure. The reaction temperature peaked at 240 ° C. inapproximately 15 minutes with continuous venting of hydrogen chloride at650 psi. Once the exothermic reaction was complete, the reaction mixturewas allowed to cool to 150 ° C. and held at that temperature for 3hours; the pressure remained constant at 250 psi. The reaction mixturewas cooled to room temperature and 1,742 grams were discharged from thereactor. A gas chromatogram of the reaction mixture showed that it wascomposed of 40.74 wt% bis(trichlorosilyl)methane.

COMPARATIVE EXAMPLE

A 22-liter reaction flask equipped with overhead mechanical stirring, apot thermometer, a reflux condenser, an addition funnel and nitrogenovergas was charged with 831 grams of toluene and 2751.5 grams oftriisopropylamine. In a separate container, 2430.6 grams of benzylchloride and 3120.4 grams of trichlorosilane were mixed in a containerand then added to the reaction mixture at a rate to maintain a reactiontemperature below reflux. Once the benzyl chloride and trichlorosilaneaddition was complete, the mixture was heated to reflux for 24 hoursafter which a gas chromatograph analysis was conducted to confirm thatthe reaction was complete. The reaction mixture was then permitted tocool to room temperature after which it was subjected to filtration. Thefilter cake was washed several times with hexane and resulted in a totalof 5050 grams of wet amine hydrochloride salts. The filtrate was thendistilled yielding 2382 grams of benzyl trichlorosilane which appearedhazy. As a result of its hazy appearance, it was concluded that thedistillation product required additional filtration, i.e., the hazeindicates the presence of a large number of byproducts, which aredifficult to separate and adversely affect the yield for thisconventional technology.

The processes of the invention produce silyl and disilyl derivativecompounds, including organochlorosilanes and dipodal silanes, includingparticularly vicinal disilyl derivatives, such as 1,2-disilyl derivativecompounds in high yield. The mixture of compounds produced from theprocesses of this invention and the yield will vary and are based onseveral factors, including the compositions of the reactants andcatalyst, as well as the operating conditions, such as process residencetime, temperature and pressure.

It is an object of this invention to provide continuous processes formanufacturing silyl and disilyl derivative compounds of organic halidesand alkenes in a manner that ensures product formation and minimizesby-product formation, thereby resulting in more efficient processescompared to those in the prior art. This is accomplished, by designingthe processes as described herein and as shown in the drawings such thatthere exists controlled exposure of reactants to the catalyst solutionat elevated temperatures and operating pressures.

The products prepared from the processes of this invention havesignificant commercial potential. However, the known uses of silanes andsilane derivative compounds produced from less efficient batch processeshave been documented and therefore are established. For example, it isknown that 1,2-disilyl derivatives, which are also products of theprocesses of this invention, are useful as coupling agents and formodifying the surface of substrates related to water repellency anddiagnostic applications. This invention provides efficient and improvedprocesses for producing silyl and disilyl derivative compounds forexisting, and possibly new, products. Examples of such products areillustrated in below:

Silane Coupling Agents

Dipodal tetrasulfide silanes are used in “green” tires, for example.

It will be appreciated by those skilled in the art that changes could bemade to the embodiments described above without departing from the broadinventive concept thereof. It is understood, therefore, that thisinvention is not limited to the particular embodiments disclosed, but itis intended to cover modifications within the spirit and scope of thepresent invention as defined by the appended claims.

1. The compound 1,2-bis(trichlorosilyl)decane.
 2. The compound 1,2-bis(trimethoxysilyl)decane.